JP2008076889A - Composition for resist underlayer film and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for resist underlayer films capable of forming a resist underlayer film excellent in adhesion to a resist film, improving the reproducibility of a resist pattern and having resistance to an alkaline liquid used for development and to oxygen ashing in resist removal, and excellent in storage stability. <P>SOLUTION: The composition for resist underlayer films contains (A) a polysiloxane having neither cyclic alkylene oxide group nor group represented by the structural formula [I]: -Ra-O-Rb and (B) a compound having a cyclic alkylene oxide group and/or a group represented by the structural formula [I], wherein Ra represents a methylene group, a 2-6C alkylene group, a phenylene group or CO; and Rb represents H or a thermally decomposable group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resist underlayer film composition and a method for producing the same, and more specifically, when forming a resist pattern on a substrate, a resist underlayer film composition for forming an underlayer film serving as an underlayer and the production thereof. Regarding the method.

In pattern formation when manufacturing semiconductor elements and the like, fine processing of a substrate made of an organic material or an inorganic material is performed by a pattern transfer method using a lithography technique, a resist development process, and an etching technique.
However, as the integration of semiconductor elements and the like on a circuit board increases, it becomes difficult to accurately transfer the pattern of the optical mask to the resist film in the exposure process. For example, it is formed in the resist film in a microfabrication process for the substrate. Due to the influence of the standing wave of the generated light, an error (inconsistency) may occur in the dimension of the formed pattern. In order to reduce the influence of such standing waves, an antireflection film is formed between the resist film and the substrate surface.
Further, when processing a substrate on which a silicon oxide film, an inorganic interlayer insulating film, or the like is processed, a resist pattern is used as a mask. However, as the pattern becomes finer, it is necessary to make the resist film and the antireflection film thinner. As the resist film becomes thinner in this way, the mask performance of the resist film decreases, and it tends to be difficult to perform desired fine processing without damaging the substrate.
Therefore, a lower layer film for processing is formed on the oxide film or interlayer insulating film of the substrate to be processed, a resist pattern is transferred to this, and the oxide film or interlayer insulating film is formed using the lower layer film for processing as a mask. A dry etching process is performed. Since the reflectance of such a processing lower layer film varies depending on the film thickness, it is necessary to adjust the composition or the like so that the reflectance is minimized according to the film thickness used. Furthermore, the processing lower layer film can form a resist pattern without skirting, has excellent adhesion to the resist, has sufficient mask properties when processing oxide films and interlayer insulating films, solution It is required to have excellent storage stability.
However, a processing underlayer film proposed so far, for example, a processing underlayer film composed of a composition containing a hydrolyzate of a specific silane compound and / or a condensate thereof (see Patent Documents 1 and 2), It was not a material satisfying all of the above characteristics, such as poor resist pattern adhesion.

JP 2000-356854 A JP-A-3-45510

  An object of the present invention is to form a resist underlayer film that has excellent adhesion to a resist film, improves the reproducibility of a resist pattern, and is resistant to an alkaline solution used for development and oxygen ashing during resist removal. Another object of the present invention is to provide a resist underlayer film composition that can be used and has excellent storage stability.

  The present inventors have intensively studied to solve the above problems. As a result, the resist underlayer film comprising a composition containing polysiloxane and a cyclic alkylene oxide group and / or a compound having a group represented by a specific structural formula improves the crosslink density after thermosetting, It has been found that by reducing the amount of residual silanol, a good resist pattern shape can be obtained on the resist underlayer film, and the adhesion with the resist is improved, and the present invention has been completed.

That is, as means for solving the above-mentioned problems, the invention described in claim 1 includes: (A) a polysiloxane having no cyclic alkylene oxide group and a group represented by the following structural formula [I]; B) A resist underlayer film composition comprising: a cyclic alkylene oxide group and / or a compound having a group represented by the following structural formula [I].

-Ra-O-Rb [I]
[In Structural Formula [I], Ra represents a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group or CO, and Rb represents a hydrogen atom or a thermally decomposable group. ]

The invention according to claim 2 is characterized in that the polysiloxane is (i) a hydrolyzate and / or condensate of a silane compound represented by the following general formula (1), and (ii) the following general formula (2). And (iii) a mixture of a silane compound represented by the following general formula (1) and a silane compound represented by the following general formula (2) The resist underlayer film composition according to claim 1, comprising at least one selected from hydrolyzate and / or a condensate thereof.
Si (OR ¹ ) ₄ (1)
[In the general formula (1), R ¹ independently represents a monovalent organic group. ]
R ² _a Si (OR ³ ) _4-a (2)
In [general formula (2), R ² is independently a hydrogen atom, a halogen atom or a monovalent organic group, R ³ represents a monovalent organic group independently, a is an integer of 1 to 3. ]

The invention according to claim 3 is the resist underlayer film composition according to claim 2, wherein at least one of R ² in the general formula (2) is a monovalent organic group having an unsaturated bond. .

The invention according to claim 4 is characterized in that the polysiloxane is
<1> (ii-1) Hydrolyzate of silane compound represented by general formula (2) and wherein at least one of R ² is a monovalent organic group having an unsaturated bond and / or condensation thereof And (iii-1) a monovalent organic compound represented by the above general formula (1) and the above general formula (2) and at least one of the above R ² has an unsaturated bond A hydrolyzate of a mixture with a silane compound as a group and / or a condensate thereof, and at least one selected from
<2> (ii-2) Hydrolyzate and / or condensate thereof of a silane compound represented by the above general formula (2) and in which R ² and R ³ do not have an unsaturated bond, and (iii) -2) A silane compound represented by the above general formula (1) and the above R ¹ does not have an unsaturated bond and the above general formula (2) and the above R ² and R ³ have an unsaturated bond. The composition for a resist underlayer film according to claim 2, comprising at least one selected from a hydrolyzate and / or a condensate of a mixture with an untreated silane compound.

  The invention according to claim 5 is the resist underlayer film composition according to claim 3 or 4, wherein the monovalent organic group having an unsaturated bond contains an aromatic ring.

  In the invention described in claim 6, the monovalent organic group having an unsaturated bond is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group, an anthryl group, a vinyl group, a styryl group, an acryloyl group, The composition for a resist underlayer film according to claim 3 or 4, comprising a methacryloyl group or a cyano group.

  The invention according to claim 7 is the resist underlayer film composition according to claim 3 or 4, wherein the monovalent organic group having an unsaturated bond contains a nitrogen atom.

  The invention according to claim 8 is the resist underlayer according to any one of claims 1 to 7, wherein the compound having the cyclic alkylene oxide group and / or the group represented by the structural formula [I] is a vinyl polymer. This is a film composition.

〔一般式（３−１）及び（３−２）において、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５はメチレン基又は炭素数２〜６のアルキレン基を示し、Ｒ^６〜Ｒ^８は互いに独立に水素原子又は炭素数１〜４のアルキル基を示し、Ａは単結合又はメチレン基を示す。〕

〔一般式（４）において、Ｒ^９は水素原子又はメチル基を示し、Ｒ^１０はメチレン基又は炭素数２〜６のアルキレン基を示す。〕 The invention according to claim 9 is characterized in that the vinyl polymer is a repeating unit represented by the following general formula (3-1), a repeating unit represented by the following general formula (3-2), and the following general formula (4). The composition for a resist underlayer film according to claim 8, comprising at least one of repeating units represented by:

[In General Formulas (3-1) and (3-2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ^{6 to} R ⁸ represent A hydrogen atom or a C1-C4 alkyl group is shown independently of each other, and A is a single bond or a methylene group. ]

In [Formula (4), R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ represents a methylene group or an alkylene group having 2 to 6 carbon atoms. ]

  The invention according to claim 10 is the compound according to any one of claims 1 to 7, wherein the compound having the cyclic alkylene oxide group and / or the group represented by the structural formula [I] is a polyfunctional crosslinking agent. This is a composition for a resist underlayer film.

  The invention according to claim 11 is the composition for a resist underlayer film according to any one of claims 8 to 10, wherein the cyclic alkylene oxide group includes an epoxy ring structure or an oxetane ring structure.

  The invention according to claim 12 is the composition for a resist underlayer film according to any one of claims 1 to 11, further comprising an acid generating compound that generates an acid by irradiation with ultraviolet light and / or heating.

  The invention described in claim 13 is a method for producing the resist underlayer film composition according to any one of claims 1 to 12, wherein the silane compound used in the resist underlayer film composition is an organic solvent. It is a manufacturing method of the composition for resist underlayer films characterized by having the process of hydrolyzing and / or condensing in presence of water and a catalyst.

  The resist underlayer film composition of the present invention has excellent adhesion to the resist film, improves the reproducibility of the resist pattern, and has resistance to an alkaline solution used for development and oxygen ashing during resist removal. A resist underlayer film can be formed, and the storage stability is excellent. Furthermore, the baking temperature for obtaining a required cured film can be set lower than before.

Hereinafter, embodiments of the present invention will be described in detail.
[1] Composition for resist underlayer film The composition for resist underlayer film of the present invention comprises (A) a polysiloxane having no cyclic alkylene oxide group and a group represented by the following structural formula [I], and (B And a compound having a cyclic alkylene oxide group and / or a group represented by the following structural formula [I].
-Ra-O-Rb [I]
[In Structural Formula [I], Ra represents a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group or CO, and Rb represents a hydrogen atom or a thermally decomposable group. ]

[(A) Polysiloxane]
As the “polysiloxane”, known polysiloxanes can be used. In addition, this polysiloxane is represented by “cyclic alkylene oxide group” and “structural formula [I]” in “(B) a compound having a cyclic alkylene oxide group and / or a group represented by structural formula [I]” described later. It does not have a “represented group”.
In the present invention, the polysiloxane includes (i) a hydrolyzate and / or condensate thereof of a silane compound represented by the following general formula (1) (hereinafter also referred to as “silane compound (1)”), (Ii) hydrolyzate and / or condensate thereof of a silane compound represented by the following general formula (2) (hereinafter also referred to as “silane compound (2)”), and (iii) silane compound (1) It is preferable to use a polysiloxane containing at least one selected from a hydrolyzate of a mixture of silane compound (2) and / or a condensate thereof.
Si (OR ¹ ) ₄ (1)
[In the general formula (1), R ¹ independently represents a monovalent organic group. ]
R ² _a Si (OR ³ ) _4-a (2)
In [general formula (2), R ² is independently a hydrogen atom, a halogen atom or a monovalent organic group, R ³ represents a monovalent organic group independently, a is an integer of 1 to 3. ]

The polysiloxane is a silane compound represented by the general formula (2) and at least one of R ² is a monovalent organic group having an unsaturated bond [hereinafter referred to as “unsaturated bond-containing silane compound ( 2-1) ". It is preferable to contain at least one component derived from
Specific examples of the component derived from the unsaturated bond-containing silane compound (2-1) include (a) a hydrolyzate and / or a condensate thereof of the unsaturated bond-containing silane compound (2-1), (b) Examples thereof include a hydrolyzate and / or a condensate of a mixture of the silane compound (1) and the unsaturated bond-containing silane compound (2-1). Among these, it is preferable to contain the hydrolyzate of an unsaturated bond containing silane compound (2-1) and / or its condensate.
When the polysiloxane contains a component derived from the unsaturated bond-containing silane compound (2-1), it is preferable in terms of low reflectivity and adhesion.

Furthermore, the polysiloxane is represented by the general formula (2) and at least one of components derived from the unsaturated bond-containing silane compound (2-1), and the R ² and R ³ are unsaturated bonds. A silane compound that does not contain [hereinafter also referred to as “non-unsaturated bond-containing silane compound (2-2)”. It is preferable to contain at least one of the components derived from Specific examples of the component derived from the non-unsaturated bond-containing silane compound (2-2) include (a) a hydrolyzate and / or a condensate of the non-unsaturated bond-containing silane compound (2-2). (B) Hydrolyzate of a mixture of a silane compound in which R ¹ in the silane compound (1) does not have an unsaturated bond and a non-unsaturated bond-containing silane compound (2-2) and / or condensation thereof Things.
Among these, at least one selected from the hydrolyzate of unsaturated bond-containing silane compound (2-1) and / or its condensate, and the hydrolysis of non-unsaturated bond-containing silane compound (2-2). It is preferable to contain at least one selected from a decomposed product and / or a condensate thereof.
When the polysiloxane contains both a component derived from the unsaturated bond-containing silane compound (2-1) and a component derived from the non-unsaturated bond-containing silane compound (2-2), low reflection From the viewpoints of adhesion, adhesion to a resist, pattern reproducibility, processing characteristics, and coating characteristics.

<Silane compound (1)>
The silane compound (1) is a compound represented by the general formula (1): Si (OR ¹ ) ₄ , and R ^{1 in} the formula is independently a monovalent organic group (however, a cyclic alkylene oxide group described later) And an alkylhydroxyl group described later). R ¹ may all be the same, or all or part of them may be different.
Examples of the monovalent organic group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a phenyl group. An alkyl group etc. are mentioned. In addition, these alkyl groups may have a substituent.

Specific examples of the silane compound (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- Examples thereof include tert-butoxysilane and tetraphenoxysilane. In addition, these silane compounds (1) may be used independently and may be used in mixture of 2 or more types.
When the silane compound (1) is used, the silicon content in the resist underlayer film composition of the present invention can be increased, and the mask resistance during etching can be improved.

<Silane compound (2)>
The silane compound (2) is a compound represented by the general formula (2): R ² _a Si (OR ³ ) _4-a , and R ^{2 in} the formula is independently a hydrogen atom, a halogen atom or a monovalent atom. An organic group (however, OR ³ group, a cyclic alkylene oxide group and an alkylhydroxyl group described later are excluded), and R ³ independently represents a monovalent organic group (however, a cyclic alkyleneoxide group and an alkylhydroxyl group described later are A) is an integer of 1 to 3.
In the case where R ² there are a plurality, to all the R ² may be the same or may be different for all or part. Also, when R ³ there are a plurality, to all R ³ may be the same or may be different for all or part.

Examples of the monovalent organic group in R ² include a monovalent organic group having an unsaturated bond and a monovalent organic group having no unsaturated bond.
The monovalent organic group having an unsaturated bond in R ² may be linear or branched. Specific examples of the monovalent organic group having an unsaturated bond include a vinyl group, an allyl group, an aryl group, a styryl group, a cinnamoyl group, a cinnamyl group, a methacryloyl group, an acryloyl group, an acetyl group, a methylidene group, and an ethylidene group. , Isopropylidene group, ethylidene group, vinylidene group, methylene group, propylene group, ethenyl group, pentenyl group, propynyl group, butenyl group, butadienyl group, isopropenyl group, butadylidene group, propadienylidene group, benzyl group, cumyl group , Mesyl group, tosyl group, xylyl group, benzylidene group, cinnamylidene group, indenyl group, pyrenyl group, acenaphthyl group, phenanthryl group, naphthyl group, anthryl group, bicyclooctenyl group, bicycloheptenyl group, bicycloundecyl group, phenyl Group, biphenyl , Terphenyl group, diphenylmethane group, aminophenyl group, stilbene group, fulvene group, camphene group, azepine group, triazine group, triazole group, azocyan group, thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group , Chloromethyl group, xanthenyl group, phenoxathiyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, isothiazolyl group, isoxazolyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, purinyl group, quinolidinyl group, isoquinolyl group Quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, carbazoyl group, phenanthridinyl group, acinidinyl group, perimedinyl group, furazanyl group, Noxazinyl group, pyrazonyl group, nitro group, diazo group, azide group, carboxy group, sulfo group, carbamoyl group, aldehyde group, amide group, allylamino group, keto group, ester group, formyl group, acetyl group, propionyl group, butyryl group , Valenyl group, isovalenyl group, oxalyl group, malonyl group, succinyl group, maleoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, furoyl group, lactoyl group, acetoxyl group, methanesulfonyl group, Thiocarbonyl group, isocyanate group, cyanate group, thiocyanate group, thioisocyanate group, carbamate group, carbamic acid group, carbamate group, N-propargyloxy group, isocyano group, cyano group, imino group, ketoxime group, benzylo Examples thereof include a xyl group, a naphthyloxy group, a pyridyloxy group, a (meth) acryloxyhydroxyalkylamino group, a sulfonyldioxy group, a carbonyldioxy group, and a monovalent organic group containing these groups.
Among these, a vinyl group, a styryl group, an acryloyl group, a methacryloyl group, a group containing an aromatic ring, and a group containing a nitrogen atom are preferable.

The group containing an aromatic ring is preferably a group containing a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group or an anthryl group.
Examples of the group containing a nitrogen atom include an amide group, an allylamino group, a cyanate group, a thiocyanate group, a thioisocyanate group, an isocyanate group, a carbamic acid group, a carbamate group, a (meth) acryloxyhydroxyalkylamino group, and a cyano group. , A group containing ketoxime group, N-propargyloxy group, caprolactam structure, oxazolidinone structure, isocyanurate structure, pyrrolidone structure, aniline structure, uracil structure, cytosine structure, pyridine structure, imidazole structure, pyrrole structure, triazole structure, particularly cyano Groups are preferred.
The monovalent organic group having an unsaturated bond may be a group containing the nitrogen atom and further containing the aromatic ring.

Examples of the monovalent organic group having no unsaturated bond in R ² include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, Examples thereof include an alkyl group which may have a substituent such as a tert-butyl group, a γ-aminopropyl group, and a γ-trifluoropropyl group.

Furthermore, examples of the monovalent organic group represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a phenyl group. And an alkyl group. In addition, these alkyl groups may have a substituent.

Among the silane compounds (2), as a compound having an unsaturated bond, that is, an unsaturated bond-containing silane compound (2-1), for example,
Acetoxyethyltrimethoxysilane, acetoxyethylmethyldimethoxysilane,
Acetoxyethyldimethylmethoxysilane, acetoxyethyltriethoxysilane,
Acetoxyethylmethyldiethoxysilane, acetoxyethyldimethylethoxysilane, acetoxymethyltrimethoxysilane, acetoxymethylmethyldimethoxysilane,
Acetoxymethyldimethylmethoxysilane, acetoxymethyltriethoxysilane,
Acetoxymethylmethyldiethoxysilane, acetoxymethyldimethylethoxysilane, acetoxypropyltrimethoxysilane, acetoxypropylmethyldimethoxysilane, acetoxypropyldimethylmethoxysilane, acetoxypropyltriethoxysilane, acetoxypropylmethyldiethoxysilane,
Acetoxypropyldimethylethoxysilane,
N-3- (acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane,
(3-acryloxypropyl) trimethoxysilane,
(3-acryloxypropyl) methyldimethoxysilane,
(3-acryloxypropyl) dimethylmethoxysilane,
(3-acryloxypropyl) triethoxysilane,
(3-acryloxypropyl) methylethoxysilane,
(3-acryloxypropyl) dimethylethoxysilane,
3- (N-allylamino) propyltrimethoxysilane,
3- (N-allylamino) propylmethyldimethoxysilane,
3- (N-allylamino) propyldimethylmethoxysilane,
3- (N-allylamino) propyltriethoxysilane,
3- (N-allylamino) propylmethyldiethoxysilane,
3- (N-allylamino) propyldimethylethoxysilane,
Allyl (chloropropyl) dimethoxysilane,
Allyl (chloropropyl) diethoxysilane,
Allyl [(3-cyclohexenyl-2-ethyl)] dimethoxysilane,
Allyl [(3-cyclohexenyl-2-ethyl)] diethoxysilane,
Allyldimethoxysilane, allyldiethoxysilane,
Allylmethyldimethoxysilane, allylmethyldiethoxysilane,
Allyldimethylmethoxysilane, allyldimethylethoxysilane,
Allylhexyldimethoxysilane, allylhexyldiethoxysilane,
Allyloxytrimethoxysilane, 2-allyloxyethylthiomethyltrimethoxysilane, O-allyloxy (polyethyleneoxy) trimethoxysilane,
Allylphenyldimethoxylane, allylphenyldiethoxysilane,
(Aminoethylaminomethyl) phenethyltrimethoxysilane,
(Aminoethylaminomethyl) phenethyltriethoxysilane,
3- (m-aminophenoxy) propyltrimethoxysilane,
3- (m-aminophenoxy) propyltriethoxysilane,
m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane,
p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane,
Benzoyloxypropyltrimethoxysilane,
Benzoylpropyltriethoxysilane,
Benzyltrimethoxysilane, benzyltriethoxysilane,
Benzylmethyldimethoxysilane, benzylmethyldiethoxysilane,
Benzyloxytrimethoxysilane, benzyloxytriethoxysilane,
5- (bicycloheptenyl) trimethoxysilane,
5- (bicycloheptenyl) triethoxysilane,
5- (bicycloheptenyl) methyldimethoxysilane,
5- (bicycloheptenyl) methyldiethoxysilane,
5- (bicycloheptenyl) dimethylmethoxysilane,
5- (bicycloheptenyl) dimethylethoxysilane,
Bis (cyanopropyl) dimethoxysilane, bis (cyanopropyl) diethoxysilane, bis (N-methylbenzamido) ethoxymethylsilane,
Bis (trimethoxysilyl) acetylene, bis (triethoxysilyl) acenaphthylene, bis (triethoxysilyl) ethylene, bis (trimethoxysilyl) ethylene,
Bis (triethoxysilyl) 1,7-octadiene,
Bis [3- (triethoxysilyl) propyl] urea,
Bis (trimethoxysilylethyl) benzene,
Bis (triethoxysilylethyl) benzene,
Bromophenyltrimethoxysilane,
Butenyltrimethoxysilane, butenyltriethoxysilane,
Butenylmethyldimethoxysilane, butenylmethyldiethoxysilane,
2- (chloromethyl) allyltrimethoxysilane,
2- (chloromethyl) allyltriethoxysilane,
(Chloromethylphenyl) ethyltrimethoxysilane,
(Chloromethylphenyl) ethyltriethoxysilane,
(Chloromethylphenyl) ethylmethyldimethoxysilane,
(Chloromethylphenyl) ethylmethyldiethoxysilane,
Chloromethylphenyltrimethoxysilane, chloromethylphenyltriethoxysilane, chloromethylphenylmethyldimethoxysilane,
Chloromethylphenylmethyldiethoxysilane,
Chlorophenyltriethoxysilane, chlorophenyltrimethoxysilane,
2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane,
2- (4-chlorosulfonylphenyl) ethyltriethoxysilane,
3-cyanobutyltrimethoxysilane, 3-cyanobutyltriethoxysilane,
(3-cyanobutyl) methyldimethoxysilane, (3-cyanobutyl) methyldiethoxylane,
2-cyanoethylmethyldimethoxysilane, 2-cyanoethylmethyldiethoxysilane,
2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane,
3-cyanopropylmethyldimethoxysilane, 3-cyanopropylmethyldiethoxysilane,
3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane,
3-cyanopropylphenyldimethoxysilane,
3-cyanopropylphenyldiethoxysilane,
11-cyanoundecyltrimethoxysilane,
[2- (3-cyclohexenyl) ethyl] dimethylmethoxysilane,
[2- (3-cyclohexenyl) ethyl] dimethylethoxysilane,
[2- (3-cyclohexenyl) ethyl] methyldimethoxysilane,
[2- (3-cyclohexenyl) ethyl] methyldiethoxysilane,
[2- (3-cyclohexenyl) ethyl] trimethoxysilane,
[2- (3-cyclohexenyl) ethyl] triethoxysilane,
Cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane,
Cyclooctenyltrimethoxysilane, cyclooctenyltriethoxysilane,
(3-cyclopentadienylpropyl) triethoxysilane,
Diallyldimethoxysilane, diallyldiethoxysilane,
Dibenzyloxydimethoxysilane, dibenzyloxydiethoxysilane,
Dichlorophenyltrimethoxysilane, dichlorophenyltriethoxysilane,
Dimethoxydivinylsilane, diethoxydimethylsilane,
1,1-diethoxy-1-silacyclopent-3-ene,
Diethyl phosphate ethyltriethoxysilane,
Dimesityldimethoxysilane, dimesityldiethoxysilane,
Dimethoxyphenylphenyl-2-piperidinoethoxysilane,
Dimethylethoxyethynylsilane,
3- (2,4-dinitrophenylamino) propyltriethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane,
Diphenylmethylethoxysilane,
Diphenylphosphinoethyldimethylethoxysilane,
Diphenylphosphinoethyltriethoxysilane,
Di (p-tolyl) diethoxysilane,
1,3-divinyltetraethoxydisiloxane,
(Furfuryloxymethyl) triethoxysilane,
5-hexenyltrimethoxysilane, 5-hexenyltriethoxysilane,
2-hydroxy-4- (3-triethoxysilylpropoxy) diphenyl ketone,
3-isocyanatopropyldimethylmethoxysilane,
3-isocyanatopropyldimethylethoxysilane,
3-isocyanatopropyltrimethoxysilane,
3-isocyanatopropyltriethoxysilane,
O- (methacryloxyethyl) -N- (triethoxysilylpropyl) urethane,
N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane,
(Methacryloxymethyl) dimethylmethoxysilane,
(Methacryloxymethyl) dimethylethoxysilane,
Methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyldimethoxysilane, methacryloxymethyldiethoxysilane,
(Methacryloxypropyl) dimethylmethoxysilane,
(Methacryloxypropyl) dimethylethoxysilane,
Methacryloxypropyltrimethoxysilane,
Methacryloxypropyltriethoxysilane,
Methacryloxypropylmethyldimethoxysilane,
Methacryloxypropylmethyldiethoxysilane,
Methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane,
Methoxyphenylmethyldimethoxysilane, methoxyphenylmethyldiethoxysilane, methylphenethylmethyldimethoxysilane, methylphenethylmethyldiethoxysilane, 1,7-octadienyltriethoxysilane,
Octenyltrimethoxysilane, octenyltriethoxysilane,
7-octenyldimethylmethoxysilane, 7-octenyldimethylethoxysilane,
Phenethyltrimethoxysilane, phenethyltriethoxysilane,
Phenethyldimethylmethoxysilane, phenethylmethylethoxysilane,
3-phenoxypropyltrimethoxysilane,
3-phenoxypropyltriethoxysilane,
m-phenoxyphenyldimethylmethoxysilane,
m-phenoxyphenyldimethylethoxysilane,
N-phenylaminopropyltrimethoxysilane,
N-phenylaminopropyltriethoxysilane,
Phenyldimethoxysilane, phenyldiethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane,
Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane,
Phenyldimethylmethoxysilane, phenyldimethylethoxylane,
N-1-phenylethyl-N′-triethoxysilylpropylurea,
(3-phenylpropyl) dimethylmethoxysilane,
(3-phenylpropyl) dimethylethoxysilane,
(3-phenylpropyl) methyldimethoxysilane,
(3-phenylpropyl) methyldiethoxysilane,
O- (propargyloxy) -N- (triethoxysilylpropyl) urethane,
Styrylethyltrimethoxysilane, styrylethyltriethoxysilane,
3-thiocyanate propyltrimethoxysilane,
3-thiocyanate propyltriethoxysilane,
p-tolyltrimethoxysilane, p-tolyltriethoxysilane,
Tribenzylmethoxylane, tribenzylethoxysilane,
2- (trimethoxysilyl) ethylpyridine, 2- (triethoxysilyl) ethylpyridine,
3- (triethoxysilylpropyl) -t-butylcarbamate,
3- (triethoxysilylpropyl) -ethyl carbamate,
3- (triethoxysilylpropyl) -methylcarbamate,
N- [3- (triethoxysilyl) propyl] -2-carbomethoxyaziridine,
N- (triethoxysilylpropyl) dansilamide,
N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole,
2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane,
N- (3-triethoxysilylpropyl) gluconamide,
N- (3-triethoxysilylpropyl) -4-hydroxybutyramide,
N-triethoxysilylpropyl-O-menth carbamate,
3- (triethoxysilylpropyl) -p-nitrobenzamide,
N- (triethoxysilylpropyl) -O-polyethylene oxide urethane,
N-triethoxysilylpropylquinine urethane,
3- (triethoxysilyl) propyl succinic anhydride,
N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam,
2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine,
N- (3-trimethoxysilylpropyl) pyrrole,
N- (3-triethoxysilylpropyl) pyrrole,
Tris (3-trimethoxysilylpropyl) isocyanurate,
Tris (3-triethoxysilylpropyl) isocyanurate,
Ureapropyltriethoxysilane, ureapropyltriethoxysilane,
O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane,
Examples thereof include vinyl diphenylethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. In addition, these unsaturated bond containing silane compounds (2-1) may be used independently, and may mix and use 2 or more types.

Among these unsaturated bond-containing silane compounds (2-1), trialkoxysilane having a cyano group such as cyanoethyltriethoxysilane, vinyltriethoxy, etc., from the viewpoint of improving adhesion to a resist film and storage stability. Trialkoxysilane having a vinyl group such as silane, trialkoxysilane having a phenyl group such as phenyltriethoxysilane, trialkoxysilane having an isocyanate group such as 3-isocyanatopropyltriethoxysilane, and 3-thioisocyanatopropyltri Carbamates such as trialkoxysilane having a thioisocyanate group such as ethoxysilane, triethoxysilylpropylmethylcarbamate, triethoxysilylpropylethylcarbamate, triethoxysilylpropyl-t-butylcarbamate Trialkoxysilanes having a group, alkoxysilane having an N- (3- triethoxysilylpropyl) -4-amide group such as hydroxy carbamate are preferred.
In addition, from the viewpoint of an antireflection function that absorbs reflected light from the base, phenyltriethoxysilane, 3-phenoxypropyltrimethoxysilane, phenethyltriethoxysilane, benzoylpropyltriethoxysilane, benzyltriethoxysilane, bis (triethoxy Trialkoxysilane having a phenyl group such as silylethyl) benzene and methoxyphenyltriethoxysilane, and trialkoxylane having a pyridine ring such as 2- (triethoxysilylethyl) pyridine are preferable.

Moreover, as a compound which does not have an unsaturated bond among the said silane compounds (2), ie, a non-unsaturated bond containing silane compound (2-2), for example,
Trimethoxysilane, triethoxysilane, tri-n-propoxysilane,
Tri-iso-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane,
Tri-tert-butoxysilane, triphenoxysilane,
Fluorotrimethoxysilane, fluorotriethoxysilane,
Fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane,
Fluorotri-tert-butoxysilane, fluorotriphenoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane,
Methyltri-n-propoxysilane, methyltri-iso-propoxysilane,
Methyltri-n-butoxysilane, methyltri-sec-butoxysilane,
Methyltri-tert-butoxysilane, methyltriphenoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane,
Ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane,
Ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane,
Ethyltri-tert-butoxysilane, ethyltriphenoxysilane,
n-propyltrimethoxysilane, n-propyltriethoxysilane,
n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane,
n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane,
n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane,
iso-propyltrimethoxysilane, iso-propyltriethoxysilane,
iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane,
iso-propyltri-n-butoxysilane, iso-propyltri-sec-butoxysilane,
iso-propyltri-tert-butoxysilane, iso-propyltriphenoxysilane,
n-butyltrimethoxysilane, n-butyltriethoxysilane,
n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane,
n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane,
sec-butyltrimethoxysilane, sec-butyl-iso-triethoxysilane,
sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane,
sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane,
sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane,
tert-butyltrimethoxysilane, tert-butyltriethoxysilane,
tert-butyltri-n-propoxysilane, tert-butyltri-iso-propoxysilane,
tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane,
tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-trifluoropropyltrimethoxysilane,
γ-trifluoropropyltriethoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane,
Dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane,
Dimethyl-di-n-butoxysilane, dimethyl-di-sec-butoxysilane,
Dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane,
Diethyldimethoxysilane, diethyldiethoxysilane,
Diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane,
Diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane,
Diethyl-di-tert-butoxysilane, diethyldiphenoxysilane,
Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane,
Di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane,
Di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane,
Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane,
Di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane,
Di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxysilane, di-iso-propyl-di-sec-butoxy Silane,
Di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane,
Di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane,
Di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane,
Di-n-butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane,
Di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane,
Di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane,
Di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane,
Di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane,
Di-tert-butyl-di-n-propoxysilane,
Di-tert-butyl-di-iso-propoxysilane,
Di-tert-butyl-di-n-butoxysilane,
Di-tert-butyl-di-sec-butoxysilane,
Di-tert-butyl-di-tert-butoxysilane,
Di-tert-butyl-di-phenoxysilane,
Diγ-aminopropyldimethoxysilane, diγ-aminopropyldiethoxysilane,
Diγ-trifluoropropyldimethoxysilane,
Diγ-trifluoropropyldiethoxysilane,
Trimethylmonomethoxysilane, trimethylmonoethoxysilane,
Trimethyl mono-n-propoxy silane, trimethyl mono-iso-propoxy silane, trimethyl mono-n-butoxy silane, trimethyl mono-sec-butoxy silane, trimethyl mono-tert-butoxy silane, trimethyl monophenoxy silane,
Triethylmonomethoxysilane, triethylmonoethoxysilane,
Triethyl mono-n-propoxy silane, triethyl mono-iso-propoxy silane, triethyl mono-n-butoxy silane, triethyl mono-sec-butoxy silane,
Triethyl mono-tert-butoxysilane, triethylmonophenoxysilane,
Tri-n-propylmono-n-propylmethoxysilane,
Tri-n-propylmono-n-ethoxysilane,
Tri-n-propylmono-n-propoxysilane,
Tri-n-propylmono-iso-propoxysilane,
Tri-n-propylmono-n-butoxysilane,
Tri-n-propyl mono-tert-butoxysilane,
Tri-n-propyl mono-sec-butoxysilane,
Tri-n-propyl monophenoxysilane,
Tri-iso-propyl monomethoxysilane,
Tri-iso-propyl mono-n-propoxysilane,
Tri-iso-propyl mono-iso-propoxysilane,
Tri-iso-propyl mono-n-butoxysilane,
Tri-iso-propyl mono-sec-butoxysilane,
Tri-iso-propyl mono-tert-butoxysilane,
Tri-iso-propyl monophenoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane,
And bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane. In addition, these non-unsaturated bond containing silane compounds (2-2) may be used independently, and may mix and use 2 or more types.

  Among these non-unsaturated bond-containing silane compounds (2-2), methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, from the viewpoint of improving the storage stability, processability, and coatability of the composition, Ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane iso-propyltriethoxysilane, iso-propyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltrimethoxy Silane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane is preferred.

  In the case of using a monoalkoxysilane having a value of 3 or a dialkoxysilane having a value of 2 in the silane compound (2), in order to obtain a composition having the necessary curability, a It is preferable to use a trialkoxysilane having a value of 1 in combination.

  The polysiloxane in the present invention is a hydrolyzate of a mixture containing the silane compound (1) and the unsaturated bond-containing silane compound (2-1) or the unsaturated bond-containing silane compound (2-2) and / or Or when it contains the condensate, the content rate of the silane compound (1) in a mixture is 1-99 mol%, Preferably it is 5-95 mol%, An unsaturated bond containing silane compound (2-1) or non- The content rate of an unsaturated bond containing silane compound (2-2) is 1-99 mol%, Preferably it is 5-95 mol%. However, the total content of the silane compound (1) and the unsaturated bond-containing silane compound (2-1) or the total content of the silane compound (1) and the unsaturated bond-containing silane compound (2-2). Is 100 mol%. When the content ratio of each silane compound is within the above range, a resist underlayer film excellent in adhesion to the resist film, the antireflection function of the resist underlayer film, and storage stability can be formed. Moreover, the hydrolyzate of the silane compound (1) and / or its condensate, and the hydrolyzate of the unsaturated bond-containing silane compound (2-1) or the unsaturated bond-containing silane compound (2-2) and / or When mixing the condensate, it is desirable to blend so as to have the same content ratio.

  Moreover, the composition for resist underlayer films of this invention is the hydrolyzate of the mixture containing the said unsaturated bond containing silane compound (2-1) and the unsaturated bond containing silane compound (2-2), and / or its When the condensate is contained, the content ratio of the unsaturated bond-containing silane compound (2-1) in the mixture is 1 to 99 mol%, preferably 5 to 95 mol%, and the unsaturated bond-containing silane compound (2 The content of -2) is 1 to 99 mol%, preferably 5 to 95 mol%. However, the total content of the unsaturated bond-containing silane compound (2-1) and the unsaturated bond-containing silane compound (2-2) is 100 mol%. When the content ratio of each silane compound (2-1) and (2-2) is in the above range, the composition has excellent storage stability, adhesion to the resist film, antireflection function of the resist underlayer film, A resist underlayer film excellent in storage stability can be formed. Moreover, the hydrolyzate and / or its condensate of unsaturated bond containing silane compound (2-1), and the hydrolyzate and / or its condensate of non-unsaturated bond containing silane compound (2-2), Also when mixing, it is desirable to mix | blend so that it may become the same content rate.

  Moreover, the composition for resist underlayer films of this invention is a hydrolysis of the mixture containing the said silane compound (1), an unsaturated bond containing silane compound (2-1), and an unsaturated bond containing silane compound (2-2). When the product and / or the condensate thereof are contained, the content of the silane compound (1) in the mixture is 1 to 98 mol%, preferably 5 to 90 mol%, and the unsaturated bond-containing silane compound (2-1 ) Is 1 to 98 mol%, preferably 5 to 90 mol%, and the content of the unsaturated bond-containing silane compound (2-2) is 1 to 98 mol%, preferably 5 to 90 mol%. It is. However, the sum total of the content rate of a silane compound (1), an unsaturated bond containing silane compound (2-1), and a non-unsaturated bond containing silane compound (2-2) shall be 100 mol%. When the content ratio of each silane compound (1), (2-1) and (2-2) is in the above range, the composition has excellent storage stability, adhesion to the resist film, and resist underlayer film. A resist underlayer film excellent in antireflection function and storage stability can be formed. Moreover, the hydrolyzate of silane compound (1) and / or its condensate, the hydrolyzate of unsaturated bond containing silane compound (2-1) and / or its condensate, and unsaturated bond containing silane compound ( In the case of mixing the hydrolyzate of 2-2) and / or the condensate thereof, it is desirable to blend so as to have the same content ratio.

[(B) Compound having cyclic alkylene oxide group and / or group represented by structural formula [I]]
The resist underlayer film composition of the present invention contains a compound having a cyclic alkylene oxide group and / or a group represented by the following structural formula [I] (hereinafter also referred to as “compound (B)”). is there.
-Ra-O-Rb [I]
[In Structural Formula [I], Ra represents a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group or CO, and Rb represents a hydrogen atom or a thermally decomposable group. ]

Examples of the cyclic alkylene oxide group include a glycidyl group, a cyclohexyl epoxy group, an oxetanyl group, a tetrahydrofurfuryl group, and the like. Note that all or some of the hydrogen atoms in the cyclic structure portion such as an epoxy ring structure or an oxetane ring structure may be substituted with a methyl group, an ethyl group, a phenyl group, or the like.
Among these, those containing an epoxy ring structure or an oxetane ring structure are preferable from the viewpoint of ring-opening reactivity.

In addition, the heat decomposable group of Rb in the structural formula [I] is decomposed by heating (usually 50 to 250 ° C.), and the structure of the “—O—Rb” site in the structural formula [I] is It becomes "-O-H".
Specific examples of the thermally decomposable group include a t-butyl group, an ethylcyclopentyl group, a methylpropyl group, an ethylcyclohexyl group, and a methyladamantyl group.

Specific examples of the group represented by the structural formula [I] include, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxylbutyl group, a phenoxymethylhydroxyethyl group, an allyloxymethylhydroxyethyl group, a polypropylene glycol group, Examples include polyethylene glycol group, carboxyl group, t-butyloxycarbonyl group, ethylcyclopentyloxycarbonyl group, ethylcyclohexyloxycarbonyl group, methyladamantyloxycarbonyl group, hydroxyphenyl group, t-butoxyphenyl group, methylpropyloxyphenyl group and the like. It is done.
Among these, a hydroxymethyl group, a hydroxyethyl group, and a hydroxybutyl group are preferable from the viewpoint of compatibility with polysiloxane. From the viewpoint of easily generating a carboxyl group or a hydroxyphenyl group, a carboxyl group, a t-butyloxycarbonyl group, a hydroxyphenyl group, or a t-butoxyphenyl group is preferable.

  Specific examples of the compound (B) include acrylic acid, methacrylic acid, t-butyl acrylate, t-butyl methacrylate, ethyl cyclopentyl acrylate, ethyl cyclopentyl methacrylate, ethyl cyclohexyl acrylate, ethyl cyclohexyl methacrylate, methyl adamantyl acrylate, methyl adamantyl methacrylate, Examples thereof include hydroxystyrene, t-butoxystyrene, methylpropyloxystyrene and the like.

Specific examples of the compound (B) further include vinyl polymers and polyfunctional crosslinking agents.
Examples of the vinyl polymer include a repeating unit represented by the following general formula (3-1) (hereinafter referred to as “repeating unit (3-1)”) and a repeating unit represented by the following general formula (3-2). (Hereinafter referred to as “repeating unit (3-2)”) and at least one of repeating units represented by the following general formula (4) (hereinafter referred to as “repeating unit (4)”). And the like.

〔一般式（３−１）及び（３−２）において、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５はメチレン基又は炭素数２〜６のアルキレン基を示し、Ｒ^６〜Ｒ^８は互いに独立に水素原子又は炭素数１〜４のアルキル基を示し、Ａは単結合又はメチレン基を示す。〕

[In General Formulas (3-1) and (3-2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ^{6 to} R ⁸ represent A hydrogen atom or a C1-C4 alkyl group is shown independently of each other, and A is a single bond or a methylene group. ]

〔一般式（４）において、Ｒ^９は水素原子又はメチル基を示し、Ｒ^１０はメチレン基又は炭素数２〜６のアルキレン基を示す。〕

In [Formula (4), R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ represents a methylene group or an alkylene group having 2 to 6 carbon atoms. ]

Specific monomers that give the repeating units (3-1) and (3-2) include, for example, glycidyl acrylate, glycidyl methacrylate, 1-ethyl-1-methyloxetanyl acrylate, 1-ethyl-1-methyloxetanyl. Examples include methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, tetrahydrofurfuryl acrylate, and tetrahydrofurfuryl methacrylate.
In addition, when the said vinyl polymer contains both repeating unit (3-1) and (3-2), R < ⁴ > -R < ⁸ > and A in the said general formula (3-1) are respectively the said general formula ( It may be the same as or different from R ^{4 to} R ⁸ in 3-2).

  Specific monomers that give the repeating unit (4) include, for example, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, phenoxymethyl hydroxyethyl acrylate, Examples include phenoxymethyl hydroxyethyl acrylate, allyloxymethyl hydroxyethyl acrylate, allyloxymethyl hydroxyethyl acrylate, acryloyl polypropylene glycol, methacryloyl polypropylene glycol, acryloyl polyethylene glycol, and methacryloyl polyethylene glycol.

Furthermore, the vinyl polymer may contain other repeating units.
Examples of the monomer that gives other repeating units include methacryloylpropyltrimethoxysilane, methacryloylpropyltrimethoxysilane, methyl acrylate, methyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene, vinyl naphthalene, and the like.

  The method for preparing the vinyl polymer is not particularly limited. For example, it can be obtained by heating and stirring acrylic acid, hydroxyethyl methacrylate, and t-butoxystyrene in the presence of a normal radical initiator. (See Synthesis Example 5 and the like in Examples described later).

Examples of the polyfunctional crosslinking agent include sorbitol polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, diester Epoxy crosslinking agents such as glycerol polyglycidyl ether, diglycidyl terephthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutadiene diglycidyl ether, 1, 4-bis [(3-ethyl-3-oxetanylmethoxy) methyl ] Oxetane crosslinking agent of benzene.
Among these, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether and the like are preferable from the viewpoint of crosslinking efficiency.

  In addition, the compound (B) in this invention may be used independently, and 2 or more types may be mixed and used for it. In the present invention, the compound (B) can be a compound other than polysiloxane.

  In the resist underlayer film composition of the present invention, the content ratio of the compound (B) is 1 to 99% by mass when the total solid content of the polysiloxane and the solid content of the compound (B) is 100% by mass. More preferably, it is 5-95 mass%, More preferably, it is 10-90 mass%, Most preferably, it is 15-85 mass%. When the content ratio of the compound (B) is within the above range, it has excellent adhesion to the resist film, improves the reproducibility of the resist pattern, and also uses an alkaline solution used for development and oxygen ashing when removing the resist. It is possible to form a resist underlayer film having resistance to the above, and to obtain a resist underlayer film composition having excellent storage stability.

[3] Other Components The composition for a resist underlayer film of the present invention contains a compound that generates an acid by performing an ultraviolet irradiation treatment and / or a heat treatment (hereinafter also simply referred to as “acid generator”). It is preferable. By containing such an acid generator, an acid is generated in the resist underlayer film by exposing the resist or heating after the exposure, and an acid is generated at the interface between the resist underlayer film and the resist film. Supplied. As a result, a resist pattern excellent in resolution and reproducibility can be formed in the alkali development treatment of the resist film.
Examples of the acid generator include a compound that generates an acid by performing ultraviolet irradiation treatment (hereinafter also referred to as “latent photoacid generator”) and a compound that generates an acid by performing a heat treatment (hereinafter “latent”). Also referred to as “thermal acid generator”.
Examples of the latent photoacid generator include onium salt photoacid generators, halogen-containing compound photoacid generators, diazoketone compound photoacid generators, sulfonic acid compound photoacid generators, Examples thereof include sulfonate compound-based photoacid generators. Examples of the latent thermal acid generator include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts. Among these, sulfonium salts and benzothiazolium salts are used. preferable. More specific compounds include compounds described in Patent Document 1 and the like.

In addition, the composition for a resist underlayer film of the present invention may contain a crosslinking agent other than the polyfunctional crosslinking agent in order to improve film curability at low temperatures. Examples of such a crosslinking agent include tetramethoxyglycoluril, tetrabutoxyglycoluril, 1,4-butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like. These may be used alone or in combination of two or more.
Said other crosslinking agent is 0.01-50 mass parts with respect to a total of 100 mass parts of solid content of a polysiloxane, and the solid content of a compound (B), Preferably it is the quantity of the range of 0.1-30 mass parts. Used in

Furthermore, the composition for a resist underlayer film of the present invention may contain β-diketone in order to improve the uniformity of the formed coating film and the storage stability. Examples of such β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2, 4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5 -Hexafluoro-2,4-heptanedione and the like. These may be used alone or in combination of two or more.
The β-diketone is used in an amount in the range of 1 to 50 parts by mass, preferably 3 to 30 parts by mass with respect to 100 parts by mass in total of the β-diketone and the organic solvent.

  The resist underlayer film composition of the present invention may further contain components such as colloidal silica, colloidal alumina, an organic polymer (excluding the vinyl polymer), and a surfactant. As the organic polymer, for example, a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide polymer, a (meth) acrylate compound, an aromatic vinyl compound, a dendrimer, polyimide, polyamic acid, polyarylene, polyamide, Examples thereof include polyquinoxaline, polyoxadiazole, and a fluorine polymer. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing interfaces. Examples include activators.

[4] Method for Producing Resist Underlayer Film Composition The method for producing a resist underlayer film composition of the present invention comprises hydrolyzing and / or hydrolyzing the silane compound or a mixture thereof in the presence of water and a catalyst in an organic solvent. Or it has the process to condense. More specifically, the silane compound is dissolved in an organic solvent, and water is intermittently or continuously added to the solution. At this time, the catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in the added water. Moreover, the temperature for performing a hydrolysis reaction and / or a condensation reaction is 0-100 degreeC normally.

  Although it does not specifically limit as water for performing the said hydrolysis and / or condensation, It is preferable to use ion-exchange water. Moreover, the said water is used in the quantity used as 0.25-3 mol with respect to 1 mol of alkoxyl groups of the whole silane compound used, Preferably it is 0.3-2.5 mol. By using water in an amount in the above range, the uniformity of the formed coating film is not likely to be reduced, and the storage stability of the composition is less likely to be reduced.

The organic solvent is not particularly limited as long as it is an organic solvent used for this kind of application, and examples thereof include propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether and the like. .
As said catalyst, a metal chelate compound, an organic acid, an inorganic acid, an organic base, an inorganic base, etc. can be used.
Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. Specifically, compounds described in Patent Document 1 (Japanese Patent Laid-Open No. 2000-356854) and the like can be used.

  Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, Gallic acid, butyric acid, merit acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Examples include sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diaza Bicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
Of these, metal chelate compounds, organic acids and inorganic acids are preferred. The said catalyst may be used independently or may be used in combination of 2 or more type. Further, the catalyst, a total of 100 parts by weight of the silane compound relative to (SiO ₂ basis), usually from 0.001 to 10 parts by weight, preferably in a range of 0.01 to 10 parts by weight.

In the present invention, after the hydrolysis and / or condensation of the silane compound, for example, it is preferable to perform a removal treatment of reaction byproducts such as lower alcohols such as methanol and ethanol. Thereby, since the purity of the organic solvent is increased, it is possible to obtain a resist underlayer film composition having excellent coating properties and good storage stability.
The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate of the silane compound and / or the condensate thereof does not proceed. For example, the boiling point of the reaction by-product is the organic When it is lower than the boiling point of the solvent, it can be distilled off under reduced pressure.

The resist underlayer film composition of the present invention comprises the polysiloxane (hydrolyzed silane compound and / or its condensate) obtained as described above, the compound (B), and other additives as required. And can be obtained by mixing.
The resist underlayer film composition of the present invention preferably has a solid content concentration of 1 to 20% by mass, particularly 1 to 15% by mass. In order to adjust the solid content concentration, the organic solvent may be further added after removing the reaction by-product.

[5] Method for Forming Resist Underlayer Film The resist underlayer film composition of the present invention is applied to the surface of an antireflection film, for example, to form a coating film of the composition and heat-treat this coating film. In the case of containing a latent photoacid generator, a resist underlayer film can be formed by performing ultraviolet irradiation treatment and heat treatment.
As a method for applying the resist underlayer composition of the present invention, a spin coating method, a roll coating method, a dip method, or the like can be used. Moreover, the heating temperature of the coating film formed is 50-450 degreeC normally, and the film thickness after heat processing is 10-200 nm normally.
The resist underlayer film formed as described above has high adhesion to the resist film, has resistance to oxygen ashing for removing the resist developer and the resist, and provides a highly reproducible resist pattern. It is done.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[1] (A) Polysiloxane
<Synthesis Example 1 (A-1)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 16.18 g of methyltrimethoxysilane and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 14.9% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 1800. Hereinafter, this reaction product is referred to as (A-1).

<Synthesis Example 2 (A-2)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 16.18 g of tetramethoxysilane and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 14.9% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 2800. Hereinafter, this reaction product is referred to as (A-2).

<Synthesis Example 3 (A-3)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 8.18 g of tetramethoxysilane, 7.52 of methyltrimethoxysilane, and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 14.9% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 2100. Hereinafter, this reaction product is referred to as (A-3).

<Synthesis Example 4 (A-4)>
Maleic anhydride aqueous solution was prepared by dissolving 0.54 g of maleic anhydride in 10.8 g of water by heating. Next, 4.35 g of cyanoethyltriethoxysilane, 2.40 g of phenyltriethoxysilane, 12.5 g of methyltriethoxysilane, and 53.5 g of ethyl lactate were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool and then set in an evaporator, and ethanol produced during the reaction was removed to obtain a reaction product.
The solid content in the obtained reaction product was 16.1% as a result of measurement by a firing method. Moreover, the molecular weight (Mw) of the obtained product (solid content) was 1000. Hereinafter, this reaction product is referred to as (A-4).

[2] (B) Compound having a cyclic alkylene oxide group and / or a group represented by the structural formula [I]
<Synthesis Example 5 (B-1)>
To the flask were added 8.93 g of methacryloxypropyltrimethoxysilane, 4.98 g of glycidyl methacrylate, 4.56 g of hydroxyethyl methacrylate, 3.65 g of styrene and 88.76 g of propylene glycol monomethyl ether acetate (PGMEA), and a nitrogen introduction tube and a cooling tube. And stirred at 50 ° C. for 15 minutes. Thereafter, 0.32 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 18.64% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 23000. Hereinafter, this resin solution is referred to as (B-1).

<Synthesis Example 6 (B-2)> (Acrylic acid copolymer)
To the flask, 9.93 g of methacryloxypropyltrimethoxysilane, 5.21 g of hydroxyethyl methacrylate, 1.72 g of methacrylic acid, and 40.87 g of PGMEA were added, and a nitrogen introduction tube and a cooling tube were attached and stirred at 50 ° C. for 15 minutes. Thereafter, 0.65 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 19.33% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 21000. Hereinafter, this resin solution is referred to as (B-2).

<Synthesis Example 7 (B-3)> (t-butyl acrylate copolymer)
To the flask, 9.93 g of methacryloxypropyltrimethoxysilane, 5.21 g of hydroxyethyl methacrylate, 2.84 g of tert-butyl methacrylate and 43.49 g of PGMEA were added, a nitrogen introduction tube and a cooling tube were attached, and the mixture was stirred at 50 ° C. for 15 minutes. Thereafter, 0.65 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 14.68% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 24000. Hereinafter, this resin solution is referred to as (B-3).

<Synthesis Example 8 (B-4)> (Vinylphenol copolymer)
To the flask, 9.93 g of methacryloxypropyltrimethoxysilane, 4.56 g of hydroxyethyl methacrylate, 2.30 g of vinylphenol and 42.46 g of PGMEA were added, a nitrogen introduction tube and a cooling tube were attached, and the mixture was stirred at 50 ° C. for 15 minutes. Thereafter, 0.65 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 14.39% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 18000. Hereinafter, this resin solution is referred to as (B-4).

<Synthesis Example 9 (B-5)> (t-butoxystyrene copolymer)
9.93 g of methacryloxypropyltrimethoxysilane, 5.21 g of hydroxyethyl methacrylate, 3.52 g of tert-butoxystyrene and 45.07 g of PGMEA were added to the flask, a nitrogen introduction tube and a cooling tube were attached, and the mixture was stirred at 50 ° C. for 15 minutes. Thereafter, 0.65 g of 2,2-azobisisobutyronitrile was added and reacted at 75 ° C. for 6 hours, then heated to 95 ° C. and reacted for 1 hour. After completion of the reaction, the reaction solution was poured into n-heptane to solidify the polymer, and the solid content was filtered off. Then, the obtained polymer was dissolved in 80 g of PGMEA to prepare a resin solution.
The solid content in the obtained reaction product was 15.13% as a result of measurement by a firing method. Moreover, Mw of the obtained product (solid content) was 19000. Hereinafter, this resin solution is referred to as (B-5).

(B-6)
Moreover, in the present Example, the epoxy crosslinking agent (sorbitol polyglycidyl ether) which is a polyfunctional crosslinking agent was used as a compound which has a cyclic alkylene oxide group and / or an alkyl hydroxyl group. This compound is referred to as (B-6).

[3] Preparation of resist underlayer film composition
<Example 1>
2.5 g of the reaction product (A-1) obtained in Synthesis Example 1 and 0.4 g of the polyfunctional crosslinking agent (B-6), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycoluril (Other crosslinking agent) 100 mg and 30 g of propylene glycol monopropyl ether were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 2>
To 2.5 g of the reaction product (A-1) obtained in Synthesis Example 1 and 2.0 g of the resin solution (B-1) obtained in Synthesis Example 5, diphenyliodonium nonafluorobutanesulfonate (acid generator) 50 mg, tetramethoxyglycoluril (another cross-linking agent) 100 mg, and propylene glycol monopropyl ether 30 g were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition. .

<Example 3>
2.5 g of the reaction product (A-2) obtained in Synthesis Example 2 and 0.4 g of the polyfunctional crosslinking agent (B-6), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycoluril (Other crosslinking agent) 100 mg and 30 g of propylene glycol monopropyl ether were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 4>
50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator) is added to 2.5 g of the reaction product (A-2) obtained in Synthesis Example 2 and 2.0 g of the resin solution (B-1) obtained in Synthesis Example 5. 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of propylene glycol monopropyl ether were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 5>
2.5 g of the reaction product (A-3) obtained in Synthesis Example 3 and 0.4 g of the polyfunctional crosslinking agent (B-6), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycoluril (Other crosslinking agent) 100 mg and 30 g of propylene glycol monopropyl ether were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 6>
50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator) is added to 2.5 g of the reaction product (A-3) obtained in Synthesis Example 3 and 2.0 g of the resin solution (B-1) obtained in Synthesis Example 5. 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of propylene glycol monopropyl ether were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 7>
2.5 g of the reaction product (A-4) obtained in Synthesis Example 4 and 0.4 g of the polyfunctional crosslinking agent (B-6), 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator), tetramethoxyglycoluril (Other cross-linking agent) 100 mg and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 8>
50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator) is added to 2.5 g of the reaction product (A-4) obtained in Synthesis Example 4 and 2.0 g of the resin solution (B-1) obtained in Synthesis Example 5. Then, 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 9>
To 2.5 g of the reaction product (A-4) obtained in Synthesis Example 4 and 2.0 g of the resin solution (B-2) obtained in Synthesis Example 6, 50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator) Then, 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 10>
The reaction product (A-4) obtained in Synthesis Example 4 (2.5 g) and the resin solution (B-3) obtained in Synthesis Example 7 (2.0 g) were mixed with nonafluorobutanesulfonic acid diphenyliodonium (acid generator) (50 mg). Then, 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 11>
50 mg of diphenyliodonium nonafluorobutanesulfonate (acid generator) was added to 2.5 g of the reaction product (A-4) obtained in Synthesis Example 4 and 2.0 g of the resin solution (B-4) obtained in Synthesis Example 8. Then, 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Example 12>
50 g of diphenyliodonium nonafluorobutanesulfonate (acid generator) was added to 2.5 g of the reaction product (A-4) obtained in Synthesis Example 4 and 2.0 g of the resin solution (B-5) obtained in Synthesis Example 9. Then, 100 mg of tetramethoxyglycoluril (another crosslinking agent) and 30 g of ethyl lactate were added and dissolved, and this solution was filtered through a filter having a pore size of 0.2 μm to obtain a resist underlayer film composition.

<Comparative Example 1>
30 g of propylene glycol monopropyl ether was added to 5.0 g of the reaction product (A-1) obtained in Synthesis Example 1 and dissolved, and this solution was filtered with a filter having a pore size of 0.2 μm for resist underlayer film. A composition was obtained.

[4] Evaluation of compositions for resist underlayer films (Examples 1 to 8 and Comparative Example 1) The following evaluations were performed on the compositions for resist underlayer films obtained in the above Examples and Comparative Examples. The results are shown in Table 1.
(1) Adhesiveness of resist Adhesiveness between a resist underlayer film composed of a composition for a resist underlayer film as a sample and a resist film formed on the underlayer film was evaluated as follows.
First, an antireflection film material “NFC B200” (manufactured by JSR Corporation) is applied to the surface of a silicon wafer by a spin coater, dried on a 200 ° C. hot plate for 1 minute, and further on a 300 ° C. hot plate. Was used for the substrate for 1 minute to form an antireflection film having a film thickness of 300 nm. The resist underlayer film composition is applied to the surface of the antireflection film of the substrate by a spin coater, dried on a hot plate at 200 ° C. for 1 minute, and further baked on a hot plate at 250 ° C. Formed a 100 nm resist underlayer film.
Next, a resist material “ARF001S” (manufactured by JSR Corporation) was applied on the resist underlayer film and dried at 130 ° C. for 90 seconds. At this time, the resist film thickness was controlled to 300 nm. Next, using an ArF excimer laser irradiation apparatus (manufactured by Nikon Corporation), the substrate was irradiated with 32 mJ of ArF excimer laser (wavelength 193 nm) through a quartz mask having a 0.2 μm line and space pattern. The substrate was heated at 130 ° C. for 90 seconds. Subsequently, the resist pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds.
When the resist pattern formed on the substrate as described above is observed with a scanning electron microscope (SEM), the case where development and peeling of the resist pattern has not occurred is indicated as “◯”. Evaluated as “x”.

(2) Resist pattern reproducibility The resist pattern formed as described above was observed with an SEM, and there was no resist film residue at the location irradiated with the laser. The case where the pattern of the space was faithfully reproduced was evaluated as “◯”, and the case where the space pattern was not faithfully reproduced was evaluated as “X”.

(3) Evaluation of alkali resistance In the above development process, the film thickness of the resist underlayer film before immersing the substrate in the developer is compared with the film thickness of the resist underlayer film after immersing, and the difference between the two is 2 nm or less. The case of “” was evaluated, and the case of exceeding 2 nm was evaluated as “×”.

(4) Oxygen ashing resistance The resist underlayer formed as described above is subjected to oxygen ashing treatment at 300 W for 10 seconds using a barrel type oxygen plasma ashing apparatus “PR-501” (manufactured by Yamato Kagaku Co., Ltd.). The case where the difference between the film thickness of the resist underlayer film before treatment and the film thickness of the resist underlayer film after treatment was 5 nm or less was evaluated as “◯”, and the case where it exceeded 5 nm was evaluated as “x”.

(5) Storage stability of the solution The resist underlayer film composition was applied to the surface of the silicon wafer using a spin coater under the conditions of a rotation speed of 2000 rpm for 20 seconds, and then dried on a hot plate at 190 ° C. for 2 minutes. As a result, a resist underlayer film was formed. About the obtained resist underlayer film, the film thickness was measured in the position of 50 points | pieces using the optical film thickness meter (the product made by KLA-Tencor, "UV-1280SE"), and the average film thickness was calculated | required.
Further, using the resist underlayer film composition after storage at a temperature of 40 ° C. for 1 month, a resist underlayer film was formed in the same manner as described above, the film thickness was measured, and the average film thickness was obtained.
The difference (T−T ₀ ) between the average film thickness T ₀ of the underlayer film by the resist underlayer film composition before storage and the average film thickness T of the underlayer film by the resist underlayer film composition after storage is determined. The ratio [(T−T ₀ ) / T ₀ ] of the magnitude of the difference with respect to the thickness T ₀ is calculated as the film thickness change rate, and the case where the value is 10% or less is “◯”, when it exceeds 10% Was evaluated as “×”.

  As is apparent from Table 1, the resist underlayer film compositions of Examples 1 to 12 have high adhesiveness to the resist, excellent alkali resistance and oxygen ashing resistance, and a highly reproducible resist pattern. A resist underlayer film can be formed and storage stability is also excellent.

Claims (13)

(A) a polysiloxane not having a cyclic alkylene oxide group and a group represented by the following structural formula [I];
(B) A resist underlayer film composition comprising: a cyclic alkylene oxide group and / or a compound having a group represented by the following structural formula [I].

-Ra-O-Rb [I]
[In Structural Formula [I], Ra represents a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group or CO, and Rb represents a hydrogen atom or a thermally decomposable group. ] The polysiloxane is (i) a hydrolyzate of a silane compound represented by the following general formula (1) and / or a condensate thereof, and (ii) a hydrolyzate of a silane compound represented by the following general formula (2). And / or its condensate, and (iii) a hydrolyzate and / or condensate of a mixture of a silane compound represented by the following general formula (1) and a silane compound represented by the following general formula (2) The composition for a resist underlayer film according to claim 1, comprising at least one selected from among the above.
Si (OR ¹ ) ₄ (1)
[In the general formula (1), R ¹ independently represents a monovalent organic group. ]
R ² _a Si (OR ³ ) _4-a (2)
In [general formula (2), R ² is independently a hydrogen atom, a halogen atom or a monovalent organic group, R ³ represents a monovalent organic group independently, a is an integer of 1 to 3. ] The resist underlayer film composition according to claim 2, wherein at least one of R ² in the general formula (2) is a monovalent organic group having an unsaturated bond. The polysiloxane is
<1> (ii-1) Hydrolyzate of silane compound represented by general formula (2) and wherein at least one of R ² is a monovalent organic group having an unsaturated bond and / or condensation thereof And (iii-1) a monovalent organic compound represented by the above general formula (1) and the above general formula (2) and at least one of the above R ² has an unsaturated bond A hydrolyzate of a mixture with a silane compound as a group and / or a condensate thereof, and at least one selected from
<2> (ii-2) Hydrolyzate and / or condensate thereof of a silane compound represented by the above general formula (2) and in which R ² and R ³ do not have an unsaturated bond, and (iii) -2) A silane compound represented by the above general formula (1) and the above R ¹ does not have an unsaturated bond and the above general formula (2) and the above R ² and R ³ have an unsaturated bond. The resist underlayer film composition according to claim 2, comprising at least one selected from hydrolyzate and / or condensate thereof in a mixture with an untreated silane compound.   The composition for a resist underlayer film according to claim 3 or 4, wherein the monovalent organic group having an unsaturated bond contains an aromatic ring.   The monovalent organic group having an unsaturated bond includes a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group, an anthryl group, a vinyl group, a styryl group, an acryloyl group, a methacryloyl group, or a cyano group. The composition for a resist underlayer film according to claim 3 or 4, wherein the composition is a resist underlayer film composition.   The composition for a resist underlayer film according to claim 3 or 4, wherein the monovalent organic group having an unsaturated bond contains a nitrogen atom.   The composition for a resist underlayer film according to any one of claims 1 to 7, wherein the compound having the cyclic alkylene oxide group and / or the group represented by the structural formula [I] is a vinyl polymer. The vinyl polymer is a repeating unit represented by the following general formula (3-1), a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (4). The composition for a resist underlayer film according to claim 8 containing at least one kind.

[In General Formulas (3-1) and (3-2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and R ^{6 to} R ⁸ represent A hydrogen atom or a C1-C4 alkyl group is shown independently of each other, and A is a single bond or a methylene group. ]

In [Formula (4), R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ represents a methylene group or an alkylene group having 2 to 6 carbon atoms. ]   The composition for a resist underlayer film according to any one of claims 1 to 7, wherein the compound having the cyclic alkylene oxide group and / or the group represented by the structural formula [I] is a polyfunctional crosslinking agent.   The composition for a resist underlayer film according to any one of claims 8 to 10, wherein the cyclic alkylene oxide group contains an epoxy ring structure or an oxetane ring structure.   The resist underlayer film composition according to any one of claims 1 to 11, further comprising an acid generating compound that generates an acid upon irradiation with ultraviolet light and / or heating.   A method for producing a resist underlayer film composition according to any one of claims 1 to 12, wherein the silane compound used in the resist underlayer film composition is contained in an organic solvent in the presence of water and a catalyst. A process for producing a composition for a resist underlayer film, which comprises a step of hydrolyzing and / or condensing the composition.